Halogenated norbornene - methanonaphthalene compounds

ABSTRACT

Novel compositions of matter having the following structural formula:   WHERE X is halogen; Y and Y&#39;&#39; are each selected from the group consisting of halogen, lower (1-4C) alkyl, lower (1-4C) alkoxy, and halogen substituted lower (1-4C) alkoxy and alkyl radicals; and R is selected from the group consisting of H, lower (1-4C) alkyl, and halogen radicals.   D R A W I N G

Ilardo Jan. 7, 1975 HALOGENATED NORBORNENE METHANONAPHTHALENE COMPOUNDS [75] Inventor: Charles S. Ilardo, Tonawanda, NY.

[73] Assignee: Hooker Chemicals & Plastics C0rp.,

Niagara Falls, NY.

[22] Filed: Sept. 16, 1969 [21] Appl. No.: 858,536

[52] U.S. Cl. 260/648 C, 260/648 F, 260/45.7

[51] Int. Cl. C07c 17/00 [58] Field of Search 260/648 F, 648 C, 649 F, 260/649 R [56] References Cited UNITED STATES PATENTS 2,799,614 7/1957 Mark 260/648 C 2,900,377 8/1959 Fields l 260/139 2,952,710 9/1960 Fields 260/648 C 2,952,711 9/1960 Roberts l 260/649 R 3,050,567 8/1962 Schmerling 260/648 C 3,201,484 8/1965 Myers et al. 260/666 Netherlands OTHER PUBLICATIONS Ziegler et al., Chem. Abstracts 49, l3076d-l3079c (1955).

Primary Examiner-Daniel D. I-Iorwitz Attorney, Agent, or Firm-Peter F. Casella; James F. Mudd 5 7 ABSTRACT Novel compositions of matter having the following structural formula:

where X is halogen; Y and Y are each selected from the group consisting of halogen, lower (l-4C) alkyl, lower (1-4C) alkoxy, and halogen substituted lower (1-4C) alkoxy and alkyl radicals; and R is selected from the group consisting of H, lower (l-4C) alkyl, and halogen radicals.

4 Claims, N0 Drawings HALOGENATED NORBORNENE METHANONAPHTHALENE COMPOUNDS These compositions, which are especially useful as fire retardant additives in normally flammable thermoplastic materials, are prepared by reacting, in ratio, two moles of a composition having the formula:

I WE=CH2 R where R is selected from the group consisting of H, lower (l-4C) alkyl, and halogen radicals.

BACKGROUND AND SUMMARY OF THE INVENTION This invention relates generally to novel compositions of matter which may be generically identified as halogenated norbomene (norbornenyl methanonaphthalene) derivatives. Such compositions have been' found to have useful properties, particularly as flame retardant additives for normally flammable thermoplastic materials. These flame retardant additives, when blended with the thermoplastic resin prior to molding, extruding, or the like, are stable at normal processing temperatures and do not discolor the plastic or have an adverse effect on the flow characteristics thereof. Consequently, the use of the subject compositions as flame retardants has solved many of the problems which have heretofore been associated with previously known flame retardants. The latter, in many instances have been incompatible with certain polymeric materials and have often down graded the fabricating capabilities of plastic.

In general, the compositions to be described in more detail below have the general structural formula:

' dimer a halogenated cyclopentadiene are reacted with one mole of a composition having the formula:

where R is selected from the group consisting of H, lower (l-4C) alkyl radicals, andhalogen radicals.

Examples of the latter are 4-vinylcyclohexene (a of butadiene), 4-(a-chlorovinyl l chlorocyclohexene (a dimer of chloroprene), and d,llimonene (dipentene, a dimer of isoprene).

With reference to the background and state of the art of compositions of this general character, reference is made herein to an article by H. E. Ungnade and E. T. McBee entitled, The Chemistry of Perchlorocyclopentenes and Cyclopentadienes; Chemical Reviews 58(2), 249-320 (1958). This article covers in detail a large number of Diels-Alder adducts prepared from the reaction of halogenated cyclopentenes and cyclopen tadienes with various dieneophiles. There is, however, no referencein the article to any class of Diels-Alder adducts prepared with two moles of halogenated cyclopentadiene with the dienophile. Moreover, all of the dienophiles are either linear or contain only ring unsaturation, the importance of which will become clear from the description below.

Belgian Pat. No. 672,846 describes a flame retardant for polymeric compositions having the general formula:

where X is bromine, chlorine, or fluorine; Y is bromine, fluorine, chlorine, alkyl or alkoxy radicals; and Z is a tetravalent cyclic hydrocarbon radical containing at least five carbon atoms.

In the Belgian specification each example of the reactant forming the Z radical is characterized by dual unsaturation confined to the ring system. In contrast, applicants class of dienophiles may be regarded as having a divalentcyclic part and a divalent linear part, 4-vinyll-cyclohexene being the most important examples.

In US. Pat. No. 2,900,377, issued to E. K. Fields on Aug. 18, 1959, there is described an example (Example V) in which equimolar proportions of l-vinyl cyclohexene-3 (i.e., 4-vinyl-l-cyclohexene) are reacted with hexachlorocyclopentadiene. It is clear from this example, however, that only 1:1 molar adducts were formed by this reaction. Other examples cited in the Fields patent include d,l-limonene with hexachlorocyclopem tadiene; but in this case, an excess molar proportion of d,l-limonene was used as the reactant and accordingly, only a 1:] adduct is formed.

The novelty and utility of this invention resides in the fact that the subject compositions are prepared by reacting 2 moles of halogenated cyclopentadiene with 1 mole of diene (e.g., 4-vinyl-l-cyclohexene) that has partly linear unsaturation (e.g., with one vinyl group) and partly cyclic unsaturation (e.g., with one cyclohexene double bond) In this manner, a norbomene meclic diene (which are discussed at length in the Chemical Reviews article and the Belgian patent cited above) and with (2) linear dienes.(e.g., butadiene, as discussed in cited Chemical Reviews article).

. In blending the compositions to improve the flame retardant properties of plastics, it has been foundthat it is only-necessary-to use about 1 to 30 percent by weight of the additive and ordinarily only '5 to 25 percent by weight. Up to 50 percent of the additive may i be used. As an incidental benefit, these compositions also improve other certain physical properties, i.e., the brittleness is diminished, elasticity is improved, and color holding properties are also enhanced.

Accordingly, it is a principal object of the invention to provide novel compositions of matter having the general formula: y

-X y X A R A V V \X a 'H X /l J where X is -halogen; Y and Y are each selected from the group consisting of halogen, lower (1-4C) alkyl,- lower (l-4C); alkoxy, and halogen substituted lower (l-4C) alkoxy and alkyl radicals; and R is'selected from the group consisting of l-l, lower l-4C)'alkyl, and halogenra'dicals. I r

Additional objects and advantages will be apparent from reading the following detailed description.

DESCRIPTION With reference to the general class of compounds described above, a very special case of these formulations is where both the X and Y radicals are halogen and, more specifically, chlorine. This compound, which has the systematic name: 6-(1, 4', 5, 6, 7, 7-hexachloro- 5'-norbornen-2'-yl)-l,2,3,4,9,9-hexachlorol,4,4a,5 ,6,7,8,8a-oxtahydro-l ,4-methanonaphthalene.

' It is formed by the Diels-Alder reaction referred to above; and more specifically it is the reaction product of 2 moles of hexachlorocyclopentadienewith 1 mole tene; pentene;

. 4 2. Reaction'product of 4-vinyl-l-cyclohexene' and l,ldimethoxy-Z,3,4,5-tetrachlorocyclopentadiene.

3. Reaction product of hexabromocyclopentadiene and 15 4-vinyl-4-cyclohexene.

4. Reaction product of l-(B-chloroethyl) pentachlorocyclopentadiene and 4-vinyl-l-cyclohexene.

5. Reaction product of 4-(a-cliloro-vinyl)-l-chloro cy- 40 clohexene and hexachlorocyclopentadiene.

The polymers embraced within the scope of, this invention include the homopolymersand copolyrners of V unsaturated aliphatic, alicyclic and aromatic hydrocarbons. Suitable monomers are ethylene; propylene; bu-

hexene; heptene; octene; 2- methylpropenel; 3- methylbutene-l; 4-methylpentenel; 4-methylhexene-l; S-me'thylhexene-l; bicyclo- (2.2.l)-2-heptene; butadiene; pentadiene; hexadiene;

isoprene; 2,3-.dimethyl-butadiene-l ,3; Z-methyl-l ,3-

pentadiene; 4 -vinyl'cyclohexene; vinylcyclohexene;. cy-

clop'entadiene; styrene and me'thylstyrene, and the like. Other polymers'in addition to the above-described olefin polymers that are useful in the invention include polyindene, indenecoumarone resins; polymers of acrylate esters and polymers of methacrylate esters, acrylate and methacrylate resins such as ethyl acrylate, nbutyl methacrylate, isobutyl methacrylate, ethyl methacrylate and methyl methacrylate; alkyd resins and paint vehicles, such as bodied linseed oil; cellulose derivatives such as cellulose acetate, cellulose acetate butyrate, cellulose nitrate, ethyl cellulose, hydroxyethyl cellulose, methyl cellulose and sodium carboxymethyl cellulose; epoxy resins; furan resins (furfuryl alcohol or furfuralketone); hydrocarbon resins from petroleum; isobutylene resins (polyisobutylene); isocyanate resins (polyurethanes); melamine resins such as melamineforrnaldehyde and melamine-urea-formaldehyde; oleoresins; phenolic resins such as phenol-formaldehyde, phenolic-elastomer, phenolic-epoxy, phenolicpolyamide, and phenolic-vinyl acetals; polyamide polymers, such as polyamides, polyamide-epoxy and particularly long chain synthetic polymeric amides containing recurring carbon amide groups as an integral part of the main polymer chain; polyester resins such as unsaturated polyesters of dibasic acids and dihydroxy compounds, and polyester elastomer and resorcinol resins such as resorcinol-formaldehyde, resorcinolfurfural, resorcinol-phenol-formaldehyde, resorcinolpolyamide and resorcinol-urea; rubbers such as natural rubber, synthetic polyisoprene, reclaimed rubber, chlorinated rubber, polybutadiene, cyclized rubber, butadiene-acrylonitrile rubber, butadiene-styrene rubber, and butyl rubber; neoprene rubber (polychloroprene); polysulfides (Thiokol); terpene resins; urea resins; vinyl resins such as polymers of vinyl acetal, vinyl acetate or vinyl alcohol-acetatecopolymer, vinyl alcohol, vinyl-alcohol, vinyl chloride, vinyl butyral, vinyl chloride-acetate copolymer, vinyl pyrrolidone and vinylidene chloride copolymer; polyformaldehyde; polyphenylene oxide; polymers of diallyl phthalates and phthalates; polycarbonates of phosgene or thiophosgene and dihydroxy compounds such as bisphenols, phosgene, thermoplastic polymers of bisphenols and' epichlorohydrin (trade named Phenoxy polymers); graft copolymers and polymers of unsaturated hydrocarbons and an unsaturated monomer, such as graft copolymers of polybutadiene, styrene and acrylonitrile, commonly called ABS resins; ABS-polyvinyl chloride polymers, recently introduced under the tradename of Cycovin; and acrylic polyvinyl chloride polymers, known by the tradename of Kydex 100. Also included in the polymers that may be employed are poly(cyclopentadiene) acrylic rubber, polycarbonate and high. impact poly-styrene.

The polymers of the invention can be in variousphysical forms, such as shaped articles, for example, molding, sheets, rods, and the like; fibers, coatings, films and fabrics, and the like.

The halogenated Diels-Alder adducts in the present composition are desirably incorporated in the polymeric materials in an effective fire retardant amount. Generally, halogenated Diels-Alder adducts in the amount of from about to about 50 percent by weight of the polymeric composition and desirably from about However, many antimony compounds are suitable. Suitable antimony compounds include the sulfides of antimony, salts of the alkali metals of Group I of the Periodic Table, antimony salts of organic acids and their pentavalent derivatives and the esters of antimonious acids and their pentavalent derivatives. It is convenient to use sodium antimonite or potassium antimonite when it is desired to use an alkali metal salt of the antimony for compositions of this invention. US. Pat. No. 2,996,528 discloses suitable antimony salts of organic acids and their pentavalent derivatives. Compounds of this class include. antimony butyrate, antimony valerate, antimony caproate, antimony heptylate, antimony caprylate, antimony pelargonate, antimony caprate, antimony cinnamate, antimony anisateand their pentavalent dihalide derivatives. Likewise, the esters 0s antimonious acids and their pentavalent derivatives disclosed in US. Pat. No. 2,993,924 such as tris(n-octyl) antimonite, tris(2-ethylhexyl) antimonite,

tribenzyl antimonite, tris(beta-chloroe thyl) antimonite,

tris(beta-chloropropyl) antimonite, 'tris(betachlorobutyl) antimonite, and their pentavalent dihalide.

derivatives. Still other suitable organic antimony compounds are the cyclic antimonites .such as trimethylol propane antimonite, pentaerythritol antimonite and glycerol antimonite. The corresponding arsenic and bismuth compounds can also be employed in particular the oxides of arsenic and bismuth.

The components comprising the compositions of the instant invention can be mixed by any one of several methods. The additives can be introduced 'into the polymer while the latter is dissolved in a suitable solvent. This procedure is especially, useful when it is desired to mix the additives during the polymer manufac- EXAMPLE I A 1 liter flask equipped with a stirrer, condenser and thermometer was charged with 605 g. (2.2 moles) of hexachlorocyclopentadiene, 108 g. (1.0 mole) of 4- vinylcyclohexene and 166 g. of mineral spirits. The apparatus was maintained under a positive nitrogen pressure and slowly heated to a reaction mixture temperature of C. The temperature was maintained between 190 and 197C for 4 hours and then allowed to cool to room temperature. The solids which separated on cooling were filtered off and washed with xylene. After washing the solid with ethanoll96 g. were obtained with a melting point of 225-244C. Calculated for C H Cl 65.1% Cl. Found: 65.0%Cl.

EXAMPLE II A 2 liter flask equipped with a thermometer, stirrer and reflux condenser was charged with 900 g. (3.3 moles) of hexachlorocyclopentadiene, 184 g. (1.7

moles) of 4-vinylcyclohexene and 15 mg. of Ethyl Corporations antioxidant 702 [4,4'-methylene bis(2,6-ditert butylphenol)]. The reaction mixture was slowly heated to 160C. at which temperature a moderate exotherm was evident. The temperature was then maintained at.159-163C.'for 24 hours. When the reaction mixture was allowed to cool to room temperature it solidified. An oil bath was used to bring the temperature back to' 140C. and 165 g. of mineral spirits added to the reaction mixture. After cooling to room temperature the product was filtered off and washed three times with 450 ml. portions of mineral spirits.- The product was purified by two recrystallizations from xylene followed-by washing of the solid with hexane to give the product with a melting point of 222-223C. Calculated for C H Cl 65.1% C1. Found: 65.5%Cl.

EXAMPLE 111 A three liter flask equipped with a stirrer, thermometer and reflux condenser was charged with 990 g. (3.6 moles) of hexachlorocyclopentadiene, 162 g. (1.5 moles) of 4-vinylcyclohexene and15 mg. of Ethyl Corporations antioxidant 702 [4,4'-methylene bis(2,6-ditert butyl phenol)]. The reaction mixture was heated to and then held at 165175C. for 27 hours. The mixture was then cooled to 510C. and filtered. The solid obtained was washed with 4 X 500 ml. portions of hexane and then dried at 110C. The product was obtained in about a 70 percent yield. 1

EXAMPLE IV MIGRATIGN TESTING Pencil rod moldings were prepared from a gram mixture of 55 percent polypropylene, 35 percent fire retardant additive and 10 percent antimony oxide. The polypropylene compositions were dry-blended in a Wyle mill and charged into 7 millimeter glass tubes.

Pencil rod moldings were prepared by heating the polypropylene compositions under pressure in a molten salt bath.

. Duplicate pencil rods for the tire, retardant composition were heated aged for 90 days at 120 centigrade.

' Weight losses calculated as percent of fire retardant additive present in the unaged pencil rods are tabulated in the table listed below:

- Days at 120 Di-Adduct of Hexachlorocyclopentadiene Evaluation of Adducts in Thermoplastic The di-adduct of hexachlorocyclopentadiene and 4- vinylcyclohexene was evaluated as listed below in various thermoplastics. The ingredients employed were: (a) polypropylene, General Purpose, supplied in powder form by Avisun as product No. 1014; (b) polystyrene, General Purpose, supplied'by Monsanto Chemical Corporation in pellet form as Hi Flow 77; (c) poly- 8 v ethylene,"Low Density, supplied in pellet form by 13.1.

DuPont as .Alathon 58;. (d) Acrylonitrile-butadienestyrene (ABS) copolymer supplied in powder form by Marbon Corporation as Blendex 101; ('e) antimony trioxide, supplied in powder form (1' micron) by M & T Chemical Corporation as Thermoguard S. I 1

Compounding Commercial molding pellets of polystyrene and polyethylene (sources listed above) were ground to approximately 20 mesh size powder. The hexachlorocyclopentadiene di-adduct of 4-vinylcyclohexe'ne was micropul-' verized to about 5 micron particle size. The powders were blended in a twin shell tumble blender in following weight percent ratios:

Di-Adduct Polyethylene 27%. v 13% Polypropylene a 60% 27% 13% Polypropylene b 60% 40% I ABS a '70% 22% 8% ABS b 60% 40% Polystyrene 15% 5% Extrusion Blending The dry blended powder formulations were then further compounded by extrusion. In addition this. step also providesmolding pellets of conventionalform by chopping the produced extrudate strands. The extruder used was a 34inch single screw Brabender having a 20:1 L/D ratio operating at RPM at 325F.-f or both barrel zones and the )6 inch diameter single strand die..For polyethylene, however, the temperatures were 300F., but the other conditionsremained the same.

injection Molding The above produced pellets were molded into 4; X

X 5 inchfbars ina Mini-Jector plunger type injection molding machine of 36 ounce capacity. Polystyrene compositions were moldedin a 1 ounce cylinder on the same machine to prepare X 4 inch disks forelectrical testing. Plunger pressures were variable depending on the material being molded and the cylinder used. Cylinder temperatures were 350-450F. for'moldingtest specimens and up to 600F. in some casesfor' evaluation of thermal stabilities. Mold temperatures were F. for polypropylene'and F. for ABS moldings.

For polyethylene moldings, the mold was not heated but allowed only to equilibriate to ambient conditions. Testing Mechanical, electrical and flammability testing was -conducted according to 'AS'TM procedures as indi-,

cated. Oven aging wasconducted under laboratory recognized procedures. All tests were performed in triplicate (minimum) except someelectrical testings which were performed in duplicate only.

Oven aging test determines the amount of loss of the composition during an extended period at afparticular temperature. The test measures the stability of the composition.

Results Results obtained are listed and compared to controls 5 in Tables 1, n and n.

TABLE] MECHANICAL PROPERTIES OF THERMOPLASTIC COMPOSITIONS CONTAINING HEXACHLOROCYCLOPENTADIENE DIADDUCT OF 4-VINYL CYCLOHEXENE Compositions TEST ASTM ASTM D-638-64T ASTM D-790-60 By Weight D758 48 Notched Tensile Elongation IZOD lmpa'ct Strength Strength Flexual Properties Ft. lbs/in. notch (PSI) Yield Yield' Break At Yield At Break Strength Modules (PSI) I Polystyrene 80% 0.55 4310 1.2 14,000 5.25 X 10 Diadduct Sb,O 5 r 11 Polystyrene 100% 0.76 7940 3.3 16,730 9.6 X 10" Ill Polyethylene Too Soft 1630 80.5 1.127 1.99 X 10 Diadduct 27% 813,0 13% IV Polyethylene 100% Too Soft 2150 55.8 1.100 2.3 X 10 V Polypropylene 60% 0.43 4520 4110 4.9 9.6 8,540 3.10 X 10 Diadduct 27% Sb,0;, 13% V1 Polypropylene 100% 0.95 5330 2300 7.7 45.2 9,290 r 2.6 x 10 VII ABS 70% 4.64 5460 4240 4.1 22.6 8,730 2.70 X 10 Diadduct 22% 58,0 8% VIII ABS 100% 7.43 5724 4510 4.2 12.0 9020 2.50 X 10" Hardness Test Compositions ASTM D-648-56 ASTM ASTM Heat Deflection C. D-2240-68 D-785- At 66 PSI At 264 PSI Shore D Rockwell L I 80.2 74.8 92.4 101.4 11 89.3 80.3 84.6 98.2 111 398 Too Soft 51.6 Too Soft IV 46.0 Too Soft 51.6 Too Soft V 71.0 48.8 77.2 51.8 VI 105.7 56.7 78.0 64.6 VII 79.7 72.7 76.8 23.8 VIII 91.5 79.7 78.8 39.4

TABLE II OTHER PROPERTIES OF THERMOPLASTIC COMPOSITIONS CONTAINING HEXACHLORO- CYCLOPENTADIENE DIADDUCT 4-VINYL CYCLOHEXENE Compositions D-635 Flame Test Modified for Oven Aging By Weight Pencil Rod Moldings Change in Wt.

F.O.* Sec. A.G." Sec. Drip Temp. C. 500 Hrs. 1,000 Hrs.

I Polystyrene 80% 21.2 38 none 80 0.l00 0.I02

Diadduct 15% 1 511,0 5% II Polystyrene 100% 80 0.053 0.63 111 Polyethylene 60% 2.0 0 none 80 ---0.061 0.078

Diadduct 27% 817,0, 13% lV Polyethylene 100% 80 0.l2 0.l2 V Polypropylene 60% 2.0 32 none 120 l.69 3.l5

Diadduct 27% 811,0; 13% V1 Polypropylene 100% 120 0.58 -0.66 Vll ABS 1.6 14 none -0.17 0.15

Diadduct 22% Sb,0, 8% VIII ABS 80 0.24 0.28

IX Polypropylene 60% 44.2 3 none Diadduct 40% X ABS 60% 6.2 0 none Diadduct 40% 'F.O. Flame out 'A.G. After glow 3,859,371 V l 1 y l2 TABLE III ELECTRICAL PROPERTIES OF THERMOPLASTIC COMPOSITIONS CONTAINING HEXACHLOROCYCLO- PENTADIENE DIADDUCT OF 4-VINYL CYCLO- HEXENE Electrical Tests Units Polystyrene 80% Diadduct 15% Sb O, 5% 'Control 100% Polystyrene Volume Resistivity ohm-cm. w or 2.5 X I0 I w or 2.5 X I0H Surface Resistivity ohm-cm. w or 2.5 X I0 00 or 2.5 X I0" 1 60Hz 2.39 2.42 Dielectric "Hz 2.38 2.42 Constant at 10Hz v 2.43 2.43 60m 0.0005 0.0005 Dissipation 10=Hz 00005 0.0005 Factor at IOHz 0.00l4 0.0004 Dielectric Str. S/S v./mil 406 464 ,Dielectric Str. S/S v./mil 425 489 Arc. Resistance secs. 2S.6- l0] .0

What is claimed is: oxy, halogen'substituted lower alkyl and halogensubl. A compound of the formula: stituted lower alkoxy radicals; and R is selected from X the group consisting'of hydrogen, lower alkyl, and h'alogen radicals, wherein said lower alkyl and lower alkoxy range from 1 to 4 carbon atoms each. 2

l X 5 2. A compound as defined'in claim 1 in which X is Y i Y I 7 selected from the group consisting of chlorine, bro- X mine, and fluorine.

3. A compound as defined in claim 2 wherein X is chlorine; Y and'Y are chlorine; and R is hydrogen.

in which X is halogen; Y and Y are each selected from drogem the group consisting of halogenJOweralkyl', lower alk- 7 i g 4. A compound as defined in claim 2 in which R is hy- 

1. A COMPOUND OF THE FORMULA:
 2. A compound as defined in claim 1 in which X is selected from the group consisting of chlorine, bromine, and fluorine.
 3. A compound as defined in claim 2 wherein X is chlorine; Y and Y'' are chlorine; and R is hydrogen.
 4. A compound as defined in claim 2 in which R is hydrogen. 